Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/06—Aluminium compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/06—Aluminium compounds
  • C07F5/061—Aluminium compounds with C-aluminium linkage
  • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
  • C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

• the present invention relates to a process for producing an aluminoxane solution usable as a catalyst in the produc­tion of syndiotactic polystyrene (SPS) or as an olefin-­polymerization catalyst.
• SPS syndiotactic polystyrene
• the present inven­tion relates to a homogeneous aluminoxane solution free from gel components and highly active as a catalyst component.
• An alkylaluminoxane obtained by reacting an organo­aluminum compound with water has been used as a catalyst component in the polymerization of an olefin, styrene or the like.
• the alkylaluminoxane used as the catalyst com­ponent is produced by reacting an organoaluminum compound with water, drying the reaction product to form a glassy solid and adding an aromatic solvent thereto.
• the aluminoxane has a problem that since it is a condensate, it is apt to form an associated molecule and particularly when its molecular weight is high, it is difficultly soluble in an organic solvent.
• Another problem of the aluminoxane is that a gel is formed and precipitated in the solution during the storage or it is deposited on the vessel wall. Since the gel is viscous and difficultly dispersed, a uniform catalyst solution cannot be obtained. Therefore, the catalyst concentration becomes uneven or pipes are clogged during the storage or transportation through a line.
• the present invention provides a process for producing a homogeneous aluminoxane solution characterized in that an alkylaminoxane (A) obtained by reacting an organoaluminum compound with water and removing a solid residue by filtra­tion is reacted with an organoaluminum compound (C) in the presence of an aromatic hydrocarbon solvent (B).
• A alkylaminoxane
• C organoaluminum compound
• the alkylaluminoxane used as the component (A) in the present invention is obtained by reacting an organoaluminum compound with water and removing a solid residue by filtration.
• the organoaluminum compounds used herein are usually represented by the following general formula: R1 k Al(OR2)mHpX1q (I) wherein R1 and R2 each represent an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, X1 represents a halogen atom, k represents a number of 0 ⁇ k ⁇ 3, m represents a number of 0 ⁇ m ⁇ 3, p represents a number of 0 ⁇ p ⁇ 3 and q represents a number of 0 ⁇ q ⁇ 3, with the proviso that k+m+p+q is 3.
• the organoaluminum compounds of the above general formula (I) include, for example, the following compounds: When p and q are 0, the compounds are represented by the general formula: R1 k Al(OR2) 3-k wherein R1 and R2 are as defined above and k represents a number of preferably 1.5 ⁇ k ⁇ 3. When m and p are 0, the compounds are represented by the general formula: R1 k AlX1 3-k wherein R1 and X1 are as defined above and k preferably represents a number of 0 ⁇ k ⁇ 3. When m and q are 0, the compounds are represented by the general formula: R1 k AlH 3-k wherein R1 is as defined above and k preferably represents a number of 2 ⁇ k ⁇ 3.
• R1 k Al(OR2)mX1q wherein R1, R2 and X1 are as defined above and k , m and q represent numbers of 0 ⁇ k ⁇ 3, 0 ⁇ m ⁇ 3 and 0 ⁇ q ⁇ 3, respectively, with the proviso that the total of k , m and q is 3.
• the organoaluminum compound is a trialkyl­aluminum such as triethylaluminum, tributylaluminum or a combination of them. It is preferably triethylaluminum, tri-n-butylaluminum or triisobutylaluminum.
• the organoaluminum compound is a dialkylaluminum alkoxide such as diethyl­aluminum ethoxide or dibutylaluminum butoxide; an alkyl­aluminum sesquialkoxide such as ethylaluminum sesquiethoxide or butylaluminum sesquibutoxide; or a partially alkoxidized alkylaluminum having an average structure of for example, R1 2 ⁇ 5 Al(OR2) 0 ⁇ 5 .
• diethyl­aluminum chloride dibutylaluminum chloride or diethyl­aluminum bromide
• the trialkylaluminums are preferred and trimethylaluminum is particularly preferred.
• Water which is reacted with the organoaluminum compound may be ordinary water, ice, vapor or water of various water-­containing compounds such as water saturated with a solvent adsorption water of an inorganic substance or metal salt-­containing crystal water such as CuSO4 ⁇ 5H2O or Al2SO4 ⁇ nH2O.
• the alkylaluminoxanes obtained by reacting the above-­described organoaluminum compound with water include chain alkylaluminoxanes of the general formula: wherein R3 represents an alkyl group having 1 to 8 carbon atoms and m represents a degree of polymeriza­tion, and cyclic alkylaluminoxanes comprising recurring units of the general formula: wherein R3 is as defined above.
• alkylaluminoxanes have a molecular weight as determined by cryoscopic method with benzene of 500 to 4,000.
• the process of the present invention is particularly effec­tive when the alkylaluminoxane having a molecular weight of 1,000 to 4,000 is used since said alkylaluminoxane is apt to form a gel.
• the catalytic reaction product of the organoaluminum compound such as the trialkylaluminum with water comprises, in addition to the above-described chain alkylaluminoxane or cyclic alkylaluminoxane, various compounds such as the unreacted trialkylaluminum, a mixture of various condensates and complicated association products of them. Various products are formed from them depending on the conditions of the catalytic reaction of the organoaluminum compound such as the trialkylaluminum with water.
• the process for reacting the organoaluminum compound with water is not particularly limited and a known process can be employed.
• the processes are, for example, (1) process wherein the organoaluminum compound is dissolved in an organic solvent and the solution thus obtained is brought into contact with water and (2) a process wherein crystal water contained in the metal salt or the like, or adsorption water of an inorganic or organic substance is reacted with the organoaluminum compound.
• this reaction proceeds even in the absence of any solvent, it is preferably conducted in a solvent.
• the solvents suitably used include aliphatic hydrocarbons such as hexane heptane and decane, and aromatic hydrocarbons such as benzene, toluene, xylene ethylbenzene and cumene.
• the alkylaluminoxane used as the component (A) in the present invention is obtained by removing, by filtration, a solid residue such as the metal salt of the water-­containing compound after the catalytic reaction and, if necessary, removing a volatile component therefrom.
• the alkylaluminoxane (A) is reacted with the organoaluminum compound (C) in the presence of an aromatic hydrocarbon solvent (B).
• aromatic hydrocarbon solvents (B) used herein include, for example, benzene, toluene, ethylbenzene, xylene and cumene.
• the organoaluminum compounds (C) are those represented by the above general formula (I). Among them, those having a branched alkyl group having 3 to 9 carbon atoms such as isobutyl group are preferred.
• the aromatic hydrocarbon solvent (B) is added to the alkyl­aluminoxane (A), then the organoaluminum compound (C) is added thereto and the mixture is stirred to conduct the reaction.
• the order of the addition is, however, not limited thereto. Namely, both aromatic hydrocarbon solvent (B) and organoalkylaluminum compound (C) can be simultane­ously added to the alkylaluminoxane (A) or, alternatively, the organoaluminum compound (C) and then the aromatic hydrocarbon solvent (B) may be added to the alkylaluminoxane (A).
• the molar ratio of the organoaluminum compound (C) to the alkylaluminoxane (A) to be reacted is 0.01/1 to 1/1, preferably 0.01 to 0.4/1, and more preferably 0.01/1 to 0.09/1 (in terms of aluminum).
• the concentration of them in the solvent is preferably 0.01 to 5 mol/l (in terms of aluminum).
• the reaction is conducted at a temperature ranging from -40°C to 150°C, preferably from 0°C to 110°C, under a pressure ranging from reduced pressure to elevated pres­sure for 1 min to 20 h, preferably 10 min to 2 h.
• the homogeneous aluminoxane solution can be thus prepared.
• the aluminoxane solution thus obtained can be used, as it is or in combination with a transition metal compound, as catalyst component in the production of an olefinic polymer such as polyethylene, atactic polypropylene, iso­tactic polypropylene, syndiotactic polypropylene, poly­butene-1 or poly-4-methylpentene-1; ethylene/propylene copolymer; or a styrene polymer having a syndiotactic structure.
• the transition metal compound is suitably selected from the group consisting of compounds of transition metals of the Groups IVB and VIII of the periodic table depending on the kind of the intended polymer.
• the aluminoxane solution prepared by the process of the present invention has an even concentration, it does not adhere to the vessel wall and, therefore, it can be stably transported.
• the aluminoxane solution obtained by the process of the present invention has a high catalytic ac­tivity and it exhibits a particularly high activity in the production of a styrene polymer mainly having syndiotactic structure.
• the aluminoxane solution prepared by the process of the present invention forms no gel and its catalytic ac­tivity is not deteriorated during the storage.
• the homogeneous aluminoxane solution produced by the process of the present invention is effectively usable as a catalyst in the production of an olefinic polymer, styrene polymer or particularly styrene polymer having a syndiotactic structure.
• Triisobutylaluminum was added to the gel-containing alkylaluminoxane solution obtained in the above step (1) in a molar ratio of 1:1 (in terms of Al) and the obtained mixture was stirred to dissolve the gel.
• the gel-free homogeneous solution thus obtained kept its homogeneous state even after one week.
• Example 1 (1) The same procedure as that of Example 1 (1) was repeated except that the reaction temperature and the reaction time were changed to 60°C and 24 h, respectively.
• 6.5 g of the catalytic reaction product was obtained.
• the molecular weight of the product as determined by the cryoscopic method was 1900.
• 60 ml of toluene was added thereto to obtain the alkylaluminoxane solution. After leaving the solution to stand at room temperature for one day, a gel was formed in the form of a precipitate, which adhered to a part of the vessel wall.
• Triisobutylaluminum was added to the gel-containing alkylaluminoxane solution obtained in the above step (1) in a molar ratio of 1:1 (in terms of Al) and the obtained mixture was stirred to dissolve the gel.
• the gel-free homogeneous solution thus obtained kept its homogeneous state even after one week.
• Styrene was polymerized in the same manner as that of Example 1 except that the alkylaluminoxane solution obtained in the above step (2) was used to obtain 220 g of the polymer. The conversion was 48 wt. %. It was confirmed that this product was a syndiotactic polystyrene having nearly 100% stereospecificity.
• Triisobutylaluminum was added to the gel-containing alkylaluminoxane solution obtained in Example 1 (1) in a molar ratio of 1:0.1 (in terms of Al) and the obtained mixture was stirred to dissolve the gel.
• the gel-free homogeneous solution thus obtained kept its homogeneous state even after one week.
• Styrene was polymerized in the same manner as that of Example 1 (3) except that the alkylaluminoxane solution ob­tained in the above step (1) was used to obtain 213 g of the polymer. The conversion was 47.0 wt. %. It was con­firmed that this product was a syndiotactic polystyrene having nearly 100% stereospecificity.
• Triisobutylaluminum was added to the gel-containing alkylaluminoxane solution obtained in Example 2 (1) in a molar ratio of 1:0.08 (in terms of Al) and the obtained mixture was stirred to dissolve the gel.
• the gel-free homogeneous solution thus obtained kept its homogeneous state even after one week.
• Styrene was polymerized in the same manner as that of Example 2 (3) except that the alkylaluminoxane solution obtained in the above step (1) was used to obtain 261 g of the polymer. The conversion was 57.6 wt. %. It was confirmed that this product was a syndiotactic polystyrene having nearly 100% stereospecificity.
• Triisobutylaluminum was added to the gel-containing alkylaluminoxane solution obtained in Example 1 (1) in a molar ratio of 1:0.02 (in terms of Al) and the obtained mixture was stirred to dissolve the gel.
• the gel-free homogeneous solution thus obtained kept its homogeneous state even after one week.
• Styrene was polymerized in the same manner as that of Example 1 (3) except that the alkylaluminoxane solution obtained in the above step (1) was used to obtain 230 g of the polymer. The conversion was 50.1 wt. %. It was confirmed that this product was a syndiotactic polystyrene having nearly 100% stereospecificity.
• Triethylaluminum was added to the gel-containing alkylaluminoxane solution obtained in Example 1 (1) in a molar ratio of 1:0.08 (in terms of Al) and the obtained mix­ture was stirred to dissolve the gel.
• the gel-free homoge­neous solution thus obtained kept its homogeneous state even after one week.
• Styrene was polymerized in the same manner as that of Example 1 (3) except that the alkylaluminoxane solution ob­tained in the above step (1) was used to obtain 223 g of the polymer. The conversion was 48.6 wt. %. It was confirmed that this product was a syndiotactic polystyrene having nearly 100% stereospecificity.
• Styrene was polymerized in the same manner as that of Example 1 (3) except that the alkylaluminoxane solution ob­tained in the above step (1) was used to obtain 218 g of the polymer. The conversion was 47.5 wt. %. It was confirmed that this product was a syndiotactic polystyrene having nearly 100% stereospecificity.
• Styrene was polymerized in the same manner as that of Example 1 (3) except that the alkylaluminoxane solution ob­tained in the above step (1) was used to obtain 212 g of the polymer. The conversion was 46.2 wt. %. It was confirmed that this product was a syndiotactic polystyrene having nearly 100% stereospecificity.

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• 1990
  • 1990-03-08 US US07/490,338 patent/US5093295A/en not_active Expired - Lifetime
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